Epoxide compositions



United States Patent Office 3,230,202 EPOXIDE COMPGSITIONS Samuel W.Tinsley, South Charleston, and Paul S.

Starcher, Charleston, W. Va., assignors to Union Carbide Corporation, acorporation of New York No Drawing. Filed Sept. 13, 1960, Ser. No.55,729 14 Claims. (Cl. 260-785) This invention relates to epoxidecompositions. In one aspect, this invention relates to the preparationof 4- oxatetracyclo [6.2. l .0 .0 undec-9-yl derivatives. In anotheraspect, this invention relates to polymerized com positions containingthe 4-0Xatetracyclo[621.0 .0 1 undec-Q-yl unsaturated derivatives.

The polymerizable compositions of the invention can be readily handledin resin-forming operations such as coating, laminating, bonding,molding, casting, potting, and the like. These p-olyrnerizablecompositions are capable of accepting solid materials, such as fillersand pigments, for providing various effects in physical properties andcoloration. With or without such added solid materials, thepolymerizable compositions can be made to fill small intricacies ofmolds without the necessity of applying high pressures or heating tohigh temperatures, although such measures can be employed, if desired.The polymerizable compositions also can be easily spread, brushed, orsprayed by many techniques available in the paint, lacquer, and varnishindustries for making coatings and finishes. The polymerizablecompositions are capable of being accurately shaped by molds havingintricate molding surfaces and fully cured to resins carrying exactdetails of such molding surfaces. They can be also advantageouslyemployed in the potting of such fragile articles as electroniccomponents.

The curable, polymerizable compositions of the invention also can bepartially reacted at elevated temperatures to form viscous thermosettingliquids or thermosetting solids. The resulting thermosettingintermediate reaction products can be dissolved in an inertnormally-liquid organic medium and applied as heat-curable coatings. Toaid solution, the thermosetting solid products can be powdered orgranulated, if desired. The thermosetting solids also can be used asmolding powder compositions which can be converted to fully cured solidproducts by the application of heat and/ or pressure. Numerous otheruses, applications, and unexpected advantages and results will be comeapparent upon a consideration of the various embodiments of theinvention which are discussed hereinafter.

Accordingly, one or more of the following objects Will be achieved bythe practice of the invention.

It is an object of the invention to prepare novel 4- oxatetracyclo[6.2.1.0 .0 ]undec-9-yl derivatives. It is another object of theinvention to prepare novel homopolymers of 4-oxatetracyclo[621.0 .01undec-9-yl unsaturated derivatives. It is a further ob ect to providenovel compositions which can be cross-linked at various stages ofprocessing to yield complex dimensional structures. A still furtherobject of the invention is to provide resins polymerized substantiallythrough the ethylenically unsaturated group of the 4-oxatetracyclo[621.0.0 1- undec-9-yl unsaturated derivatives. Another object of theinvention is to provide resins polymerized substantially through theethylenically unsaturated group and crosslinked through the epoxy groupof the 4-oxatetracyclo- [6.2.l.0 .0 ]undec-9-yl unsaturated derivatives.Another object of the invention is to provide novel compositionsobtained by the reaction of the product resulting from the initialpolymerization through the olefinic linkage of the4-oxatetracyclo[6.2.1.0 .0 ]undec-9-y1 unsaturated derivatives and anactive organic hardener. A further object of the invention is to providenovel polymers Patented Jan. 18, 1966 obtained by the reaction of4-oxatetracyclo[-6.216 10 1- undec-9-yl unsaturated derivatives and apolymerizable unsaturated monomer having at least one ethylenicallyunsaturated, polymerizable group. A yet further object is to providenovel compositions obtained by the reaction of the product resultingfrom the initial polymerization of 4-oxatetracyclo[6.2.l.0 .0]undec-9-yl unsaturated derivatives with polymerizable unsaturatedmonomers having at least one ethylenically unsaturated polymerizablegroup and an active organic hardener. Other objects will become apparentto those skilled in the art in light of the instant specification.

In a broad aspect, the invention pertains to the novel and usefulcompositions of the invention characterized by the following generalformula:

wherein Y can represent the following radicals: halo, RO,

H ll RCO, R--C-NH- and R'SO wherein R represents a monovalenthydnocarbon radical such as alkyl, alkenyl, cycle-aliphatic rings,aromatic rings, and the like; with the proviso that when R in the ROgroup is alkenyl, the ethylenically unsaturated carbon-towarhon bond isat least one carbon atom removed from the ether oxygen atom, i.e., O;and wherein R represents a saturated hydrocarbon radical or an aromaticradical. The cycloa-li-phatic rings can be saturated and unsaturated.Preferred cycloaliphatie rings are those containing from five to sevencarbon atoms in the ring. The aliphatic hydrocarbon chains can bestraight or branched, saturated or unsaturated, said chains preferablycontaining from one to eighteen carbon atoms.

With reference to Formula I supra, illustrative Y variables include,among others, chloro, bromo, methoxy, ethoxy, isopropoxy,tertiary-butoxy, n-hexoxy, n-decoxy, 2- propenyloxy, 3-butenyloxy,Z-methyl 4-pentenyloxy, 5- hexenyloxy, S-decenyloxy, cyclopentoxy,Z-cyclopentenyloxy, cyclohexoxy, 3-cyclohexenyloxy, cyclohept-oxy, 4-cyclohetptenyloxy, phenoxy, benzyloxy, formyloxy, acetytloXy,n-hexanoyl-oxy, S-methyl-hexanoyloxy, n-dodecanoyloxy, acryloyloxy,3-propenoxyloxy, 6-heptenoyloxy, 9- heptadecenoyl-oxy, benzoyloxy,cyclohexanecarbonyloxy, 3-cyclohexenecarbonyloxy,cyclopentanecarbonyloxy, 2- cyclopentenecarbonyloxy,cyclopentanecarbonyloxy, 2- cyclopentenecarbonyloxy,cycloheptanecarbonyloxy, 4- cycloheptenecarbonyloxy, alkylsubstituted-cyclohexanecarb onyloxy, alkylsubstituted-cyclopentanecarbonyloxy, alkylsubstituted-cyclopentenecarbonyloxy, formamido, acetamido, pnopionamido,heptanamido, heptadecanamido, acrylamido, Z-butenamido, B-pentenamid'o,9-decenarnido, benzamido, cyclohexylformam-ido, 3-cyclohexenylformamidolalkyl substituted-cyclohexylfiormamido, alkylsubstituted-3-cyclohexenylformamid=o, methylsulfonyl, ethylsulfonyl,propylsulfonyl, n-hexylsulfonyl, n-octadecylsulfonyl,methoxyethylsulfonyl, ethoxyethylsulfonyl, n-hexoxyethylsulfonyl,n-octoxyloctylsulfonyl, n-nonoxynonylsulfonyl, phenylsulfonyl,phenylethylsulfonyl, cyclohexylsulfonyl, cyclopentylsulfonyl,naphthylsulfonyl, and the like. Representative R radi cals include forinstance, ethyl, pnopyl, butyl, amyl and the like.

of the tricyclo[5.2.1.O ]3-decen-8-yl radical. The quantity of peracidconsumed during the course of the reaction can be readily determined bywell-known procedures. To effect substantially complete epoxidation ofthe tricyclo[S.2.l.0 ]-3-decen-8-yl radical, at least a stoichiometricquantity of peracid per carbon-to-carbon double bond :of said radicalshould be employed. If, however, other carbon-to-carbon double bonds arepresent in a radical of the compound, other than the tricyclo- [5.2.1.0]-3-decen-S-y1 radical, only a stiochiometric quantity or less percarbon to carbon double bond of the tricyclo[5 2.1.0 -3-decen-8-ylradical is used to introduce the oxirane oxygen in the tricyclo[5.2.1.0]3-decen-8- yl radical. The inert normally-liquid organic vehicle andacid by-product can be recovered from the reaction product mixture, forexample, by distillation under reduced pressure. If desired, the residueproduct can be subjected to fractional distillation, crystallization,and the like to obtain the monoepoxide product in high purity.

The unsaturated starting compounds which are used in the preparation ofthe monoepoxides of the invention can be prepared, for example, by theaddition of compounds such as alkenoic acids, alkenols, cycloalkanols,cycloalkerrols, cycloalkanoic acids, alkanamides, aryl mercaptans, alkylmercaptans, hydrochloric acid, and the like, to dicyclopentadiene, andheating the resulting mixture, e.g., about C., and lower, to about 150C., and higher. The reaction is conducted in the presence of a smallquantity of inorganic acidic catalyst such as sulfuric acid, borontrifluoride, or boron trifluoride complexes with water, ether, amines,and the like. The resulting reaction mixture can be washed with waterand soda solution, dried, and distilled under reduced pressure to thusrecover the desired unsaturated product.

The novel monoepoxides of the invention are useful as modifying andplasticizing agents for various synthetic condensation resins and arealso useful as stabilizers for various synthetic resins. Due to thepresence of the vicinal epoxy group the novel compounds of the inventionpossess useful solvent properties. For example, they are compatible withmany vinyl chloride and vinylidene chloride resins. Accardingly, thecompounds of the invention can be used as plasticizers for these andother resins. By incorporating into the resin from about to 50 percentby Weight of these novel epoxides, a plasticized product is obtainedwhich possesses useful resilient and flexible characteristics. The vinylhalide resins which can be satisfactorily plasticized by the compoundsof this invention are, for example, poly(vinyl chloride), vinylchloride-vinyl acetate copolymers, vinyl chloride-acrylonitrilecopolymers, vinyl chloride-vinylidene chloride-acrylonitrile copolymersand the like. The compounds of this invention may be used alone or inconjunction with the conventional plasticizers. In addition to their useas plasticizers, the compounds of this invention can be employed asstabilizers for chlorinecontaining resins where they are efiective evenat low con centrations.

Of particular significance, the novel 4-oxatetracyclo- [6.2.l.O .O]undec-9-yl unsaturated derivatives of the invention are highly usefulin the preparation of polymerized products. The 4-oxatetracyclo[6.2.l0.0 undec- 9-yl unsaturated derivatives are characterized by the presenceof one vicinal epoxy group and one ethylenic group, C-=C The presence oftwo functional groups in the one molecule makes them highly useful forthe preparation of cross-linked resin structures. For example, the novelepoxides can be polymerized through the ethylenic groups with each otheror with other vinyl monomers through the ethylenic grouping in thepresence of a suitable peroxide catalyst to form soluble, fusible,linear polymers and further cured with an active organic hardener orcross-linked through the epoxide grouping in the presence of basic oracidic epoxide catalysts if desired, to form insoluble, infusiblecompositions. In another manner, the 4-oxatetracyclo- [6.2.l.0 .0]undec-9-yl unsaturated derivatives of the invention can be polymerizedthrough the epoxide groups with or without the presence of a suitablebasic or acidic epoxide catalyst and cross-linked in the presence ofsuitable peroxide catalyst through the unsaturated ethylenic group toform insoluble, infusible compositions.

It should be noted that at this time that the expression peroxidecatalysts as used herein, refers to those catalysts, hereinafterdescribed, used in the polymerization of the compounds of the inventionthrough the available unsaturated ethylenic groups. Moreover, theexpression basic or acidic epoxide catalyst as used herein, refers tothose catalysts, hereinafter described, used in the polymerization ofthe compounds of the invention through the available epoxy groups,

The expression active organic hardeners" indicates those compounds whichwhen reacted with available epoxy groups cause a curable systemcomprising poly-epoxide(s) to become a thermosetting or thermoset resinin accordance with the teachings of the instant specification.Representative active organic hardeners include polycarboxylic acids,polycarboxy polyesters, polycarboxylic anhydrides, polyols, e.g.,polyhdric phenols and polyhydric alcohols, polyfunctional amines,polythiols, polyisocyanates, polyisothiocyanates, polyacryl halides andthe like.

The 4-oxatetracyclo[6.2.l.O .0 ]undec-9-yl unsaturated dcrivatives arethose compounds described in Formula I, supra, having an ethylenicunsaturated hydrocarbon radical attached to the functional groups suchas attached in the nine-carbon position of the 4-oxatetracyclo[6.2.1.O.0 ]undec-9-yl radical. Typical subclasses of 4-oxatetracyclo[6.2.l.0 .0]undec-9-yl unsaturated derivatives of the invention include, forinstance,

alkenyl 4 oxatetra-cyclo[6.2.1.O .0 ]undec-9-yl ethers wherein theethylenic unsaturation is at least one carbon removed from the etheroxygen, i.e., O,

cycloalkenyl 4-oxatracyclo[621.0 .0 1undec-9-yl ethers,

4-oxatetracyclo [6.2.1.O. .0 ]undec-9-yl alkenoates,

N-(4-oxatetracyclo[6.2.10 .0 ]undec-9-yl) alkenamides,

N-(4-oxatetracyclo [621.0 .0 undec-9-yl)cycloalkenecarboxamides,

and the like.

Specific 4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl unsaturated derivativesinclude, for instance,

allyl 4-oxatetracyclo[6.2.l.0 .0 ]undec-9-yl ether,

crotyl 4-oxatetracyclo[621.0 .0 ]undec-9-yl ether,

3-butenyl 4-oxatetracyclo [6.2. 1 .0 .0 ]undec-9-yl ether,

S-hexenyl 4-oxatetracyclo[6.2.1.0. .0 ]undec-9-yl ether,

2-cyclopentenyl 4-oxatetracyclo[6.2. 1.0 .0 undec-9-yl ether,

3 -cyclohexenyl 4-oxatetracyclo[6.2.1.0. .0 ]undec-9-yl ether,

7 4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl acrylat e,4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl crotonate,4-oxatetracyclo[6.2.1.O. .0 ]undec-9-yl undecylenate,4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl l t-cyclohexenecarboxylate,

N-(4-oxatetracyclo [6.2.1.0 ".O ]undec-9-yl) acrylamideN-'(4-oxatetr-acyclo 6.2. 1 .0 undec-9-yl) -3-butenamide,

N- (4 oxatetracyclo [6 .2. 1 .0 .0 undec-9-yl) -l O-undecanamide,

N-(4-oxatetracyc1o[6.2. l.0 .0 ]undec-9-yl) -3-cyclohexenecarboxamideand the like.

Accordingly, the first preferred embodiment of the invention is directedto novel homopolymeric products which are prepared by effecting thepolymerization of 4-oxotetracyclo-[6.2.1.0 .0 ]undec 9 yl unsaturatedderivatives. A useful subclass of the homopolymeric products of theinvention is obtained by the polymerization of 4-oxatetracyclo[6.2.1.0.0 ]undec-9-yl unsaturated derivatives through the epoxy group in thepres ence of an acidic or basic epoxide catalyst, described hereinafter.The novel polymeric products of this subclass are characterized by thepresence of free ethylenic groups. The useful polymeric productsobtained can range from viscous liquids to hard, linear, fusible resins.Additionally, the polymerized products of the above subclass can befurther polymerized through the available ethylenic groups in thepresence of a peroxide catalyst, hereinafter described, to obtain ahard, cured resin. A second useful subclass of the homopolymericproducts of the invention is obtained by the polymerization of4-oxatetracyclo[6.2.1.O .0 ]undec-9-yl unsaturated derivatives throughthe ethylenically unsaturated group in the presence of a peroxidecatalyst, described hereinafter. The novel polymeric products of thesecond subclass are characterized by the presence of free epoxy groups.The novel polymeric products of the second subclass are characterized bythe presence of free epoxy groups. These polymeric products are useful,fusible compositions. Additionally, the polymerized products of thissubclass can be further polymerized through the available epoxy groupsin the presence of an acidic or basic epoxy catalyst, hereinafterdescribed. These latter polymeric products are useful, infusiblecompositions.

The second embodiment of the invention is directed to novel copolymericproducts of 4-oxatetracyclo 6210 .0 -undec-9-y1 unsaturated derivatives.A useful subclass of the copolymers of the invention is obtained by thepolymerization of 4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl unsaturatedderivatives with vinyl monomers which contain at least one polymerizableethylenic unsaturated bond, through the ethylenicallyunsaturated groupin the presence of a peroxide catalyst, described hereinafter.

Additionally, the polymerized products of the above subclass can befurther polymerized through the available epoxy groups in the presenceof an acid or base epoxide catalyst. A second useful subclass of thecopolymeric products of the invention is obtained by thehomopolymerization of 4-0ctatetracyclo[6.2.1.O 0 undec-9-yl unsaturatedderivatives through the epoxy group in the presence of an acidic orbasic epoxide catalyst and further polymerization with vinyl monomerswhich contain at least one polymerizable ethylenically unsaturated bond,through the ethylenically unsaturated group in the presence of aperoxide catalyst. Suitable polymerizable vinyl monomers include thearomatic monomers which contain ethylenically unsaturated side chainssuch as styrene, chlorostyrene, allylstyrene and the like. Other typicalgroups of ethylenically unsaturated monomers include vinyl chloride,vinyl bromide,

vinyl fluoride, acrylonitrile, methacrylonitrile, vinylidene chloride,vinylidene bromide, vinylidene fluoride. Other typical groups ofpolymerizable ethylenically unsaturated monomers include: a vinylesterof an aliphatic monocarboxylic acid, for example, vinyl acetate,vinyl butyrate, vinyl chloroacetate, vinyl formate, vinyl caproate, andthe like; unsaturated aliphatic esters of a saturated aliphaticpolybasic acid or an unsaturated aliphatic ester of an unsaturatedaliphatic polybasic acid or unsaturated esters of dibasic aromatic acidsfor example, the divinyl, dialkyl, and dimethallyl esters of oxalicacid, maleic acid, citric acid, and tartaric acid; the divinyl, diallyland methallyl esters of phthalic acid, isophthalic acid, terephthalicacid, and naphthalenedicarboxylic acid; monomers having a conjugatedsystem of ethylenic double bonds, for instance 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, l-acetoxy-butadiene, 2-cyano-1,3-butadieneand the like. Other suitable polymerizable monomers include unsaturatedaliphatic ethers of saturated polyhydric alcohols, for instance,divinyl, dialkyl and dimethallyl ethers of glycol and the like. Thepolymerization products of this embodiment can range from a viscousliquid to a solid.

The third embodiment of the invention is directed to novel polymericproducts resulting from the polymerization of 4-oxatetracyclo[6.2.1.0 .O]undec-9-yl unsaturated derivatives with other epoxides through theepoxy group in the presence of an acidic or basic epoxide catalyst,described hereinafter. The resulting polymeric compositions contain aplurality of ethylenic groups. Suitable epoxides which can be reactedwith 4-oxatetracyclo[621.0 .0 1undec-9-yl unsaturated derivativesinclude: Polyepoxides such as limonene dioxide, 4-vinylcyclohexenedioxide, dicyclopentadiene dioxide, divinylbenzene dioxide,3,4-epoxy-6-methylcyclohexylmethy1 3,4-epoxy 6methylcyclohexanecarboxylate, diethylene glycolbis(3,4-epoxycyclohexanecarboxylate), bis(2,3- epoxycyclopentyl) ether,bis(3,4-epoxycyclohexylmethyl) pimelate, 1,1,1-trimethylolpropanetri-s(3,4-epoxy cyclohexanecarboxylate), the polyglyci-dyl polyethers ofpolyhydric phenols and the like. The resulting products of thisembodiment are useful fusible compositions. Additionally, the polymericproducts of this embodiment can be further polymerized through the freeethylenic groups in the presence of an acidic or basic epoxide catalystto obtain a cross-linked, insoluble, infusible composition.

The fourth embodiment of the invention is directed to novel polymericproducts resulting from the polymerization of vinyl monomers whichcontain at least one polymerizable ethylenically unsaturated bond, asdescribed in the second embodiment with the polymeric product of thethird embodiment, i.e., the polymerization of 4- oxatetracyrclo 6.2. 1 0.0 undec-9-yl unsaturated derivatives with other epoxides, through theepoxy groups. The instant polymerization can be conducted in thepresence of an acidic or basic epoxide catalyst to obtain a crosslinked,infusible polymeric product.

The fifth embodiment of the invention is directed to a novel polymericproduct resulting from the polymerization of the copolymer of the secondembodiment, first subclass, and the epoxides, as described in the thirdembodiment, in the presence of an acidic or basic epoxide ca-taylst, toobtain an infusible resin.

The sixth embodiment pertains to novel curable, partially cured andcured polymeric products obtained from the reaction of thehOIIllOPOlYII1I of 4-oxatetracyclo- [6.2.1.0 .0 ]undec-9-yl unsaturatedderivative polymerized through the ethylenically unsaturated group(second subclass of the first embodiment) With an active organic(hardener in the presence of an acidic or basic epoxide catalyst,described hereinafter. The resulting products are useful partially curedand cured compositions.

The seventh embodiment pertains to novel curable, partially cured, andcured polymeric products obtained by the reaction of the oopolymer of4-oxatetracyclo- [621.0 .0 undec-9-yl unsaturated derivatives and vinylmonomers which contain at least one polymerizable ethylenicallyunsaturated bond, said copolymer polymerized through the availableethylenically unsaturated bonds (described in the second embodiment,first subclass) with an active organic hardener, in the presence of anacidic or basic epoxide catalyst, described hereinafter. The resultingproducts are useful partially cured and cured compositions.

Where an acidic or basic catalyst is employed in this invention, it isadvantageous to add said cataylst to the component(s) at a temperaturerange, for example, of from about 10 C. to about 100 C., preferably withagitation, to insure homogeneity of the resulting admixture. Catalystconcentrations can be varied over a broad range and can be selected onthe basis of the rate of polymerization desired and the polymerizationtemperature to be used. It has been found that catalyst concentrationsfrom about 0.005, or lower, to 15 weight percent, or 'higher, preferablyfrom about 0.01 to weight percent, based on the weight of the epoxidecomponent(s) used can be employed. The period of time required for thepolymerization reaction can range from several minutes to twenty-fourhours, and longer, depending on concentration of catalyst, temperature,the particluar catalyst employed, the epoxide components(s), and otherfactors.

Typical acidic and basic epoxide catalysts which can be employedinclude, for example, the metal halide Lewis acids, e.g., borontrifluoride, aluminum chloride, zinc chloride, stannic chloride, ferricchloride, boron tn'fluoridepiperidine complex, boron trifluoride1,6-hexanediamine complex, boron trifiuoride monoethylamine complex,boron trifluoride-dimethyl ether complex, boron trifluoride-diethylether complex, boron trifluoride di propyl ether complex, and the like;the strong mineral acids, e.g., sulfuric acid, phosphoric acid,polyphosphoric acid, perchloric acid, and the like; the saturatedaliphatic hydrocarbon sulfonic acids and the aromatic hydrocarbonsulfonic acids, e.g., ethanesulfonic acid, propa-nesulfonic acid,benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid,lower alkyl substituted benzenesulfonic acids, and the like; and thealkali metal hydroxides, e.g., sodium hydroxide, potassium hydroxide,and .the like.

Where peroxide cataylsts are employed in the polymeri zation through theethylenically unsaturated groups, catalyst concentrations can be variedover a bro-ad range and can be selected on the basis of the rate ofpolymerization desired and the polymerization temperature to be used.The preferred catalyst concentration can vary from 0.1 weight percent,or lower, to 5.0 weight percent, or higher, based on the total weight ofthe ethylenic componentfs) employed. The period of time required for thepolymerization reaction can range from several minutes to 40 hours, andlonger, depending on concentration of catalyst, temperature, thecatalyst employed, the ethylenic component(s) employed, and otherfactors. The temperature employed in the polymerization can vary from 0C. to about C. Preferred temperatures range from 40 C. to 80 C.Additionally, the instant polymerization reaction can be carried out insolution, emulsion, suspension, and bulk systems. Examples of organicmedia useful in a solution polymerization include acetone,tetrahydrofuran, dimethylformamide, benzene, and the like.

The peroxide catalysts used in the invention can be exemplified byace-tyl peroxide, benzoyl peroxide, benzoylacetyl peroxide,tertitary-butyl hydroperoxide, tertiarybutyl peracetate,azo-bis(isobutyronitrile), and the like.

The curable compositions of the sixth and seventh embodiments of theinvention can be prepared by mixing the corresponding homopolymer orcopolymer, used in said embodiments, with the active organichardener(s), preferably under agitation, so as to obtain a homogeneousmixture. The order of addition of the components does not appear to becritical. When a solid or highly viscous component or active organichardener is employed, heating is advantageous in facilitating theformation of a solution. In preparing homogeneous mixtures, it is ad- 10vantageous to employ a temperature as high as the melting point of thehighest melting component contained in the curable mixture. In anyevent, the application of heat should not be prolonged to the extentthat appreciable curing takes place.

The curable compositions of the sixth and seventh embodiments of theinvention can be partially cured or fully cured by maintaining thetemperature in the range of from about 10 C., and lower, to about 250C., and higher, and preferably from about 25 C. to about 200 C. A highercuring temperature generally will provide a thermosetting or thermosetresin in less time than a lower curing temperature. One preferablemethod is to heat the curable compositions to a temperature within therange from about 50 C. to 150 C. to first partially cure thecomposition. A temperature from about C. to 200 C. then can be used tocomplete the cure. However, any one or combination of two or moretemperatures within the specified range of 10 C. to 250 C. can beemployed, if desired, to effect the full cure. For casting purposes thepreferred minimum temperature of the normally solid curable compositionsis that at which said compositions form a uniform melt, whereas forcoatings and the preparation of laminates, the use of solvents willallow the use of lower temperature.

The time for effecting the partial cure or the complete cure will begoverned, to an extent, on several factors such as the particularhomopolymer of 4-oxatetracyclo- [6210 .0 undec-9-yl unsaturatedderivative(s) or copolymers employed, the particular active organichardener(s) employed, the proportions of homopolymer of4-oxatetra-cyclo-[6.2.1.0 .0 ]un-dec-9-yl unsaturated derivative(s) orcopolymers and active organic hardener(s), the inclusion of an activeorganic hardener modifier, the inclusion of a catalyst, theconcentration of the catalyst and/or modifier, the temperature foreffecting the cure, and other considerations. In general, the time foreffecting the complete cure can vary from several minutes to severaldays, e.g., from ten minutes to one week, depending upon the correlationof such factors as illustrated above.

The novel curable, partially cured, and cured compositions of the sixthand seventh embodiment of the invention comprises homopolymer orcopolymer of 4- oxatetracyclo 6.2. l .0 10 undec-9-yl unsaturatedderivative and polycarboxylic acid in such relative amounts so as toprovide from about 0.1 to about 2.0 carboxyl groups, i.e., COOH groups,of said polycarboxylic acid per epoxy group, i.e.,

groups, of homopolymer or copolymer epoxide, and preferably from about0.3 to about 1.2 carboxyl groups per epoxy group.

Rrepresentative polycarboxylic acids which can be employed include, forexample, oxalic acid, glutaric acid, suberic acid, alkylsuccinic acids,alkenylsuccinic acids, maleic acid, glutaconic acid, allylmalonic acid,3-hexynedioic acid, 1,Z-cyclohexanedi-carboxylic acid, .ph-th-alic acid,terephthalic acid, and the like.

Other novel curable, partially cured, and cured com positions of thesixth and seventh embodiments of the invention comprises homopolymer orcopolymer of 4- oxatetracyclo- 6 .2. 1 0 .0 undec-9-yl unsaturatedderivative and polycarboxylic acid anhydride in such relative amounts soas to provide from about 0.1 to about 4.0 carboxyl groups of thepolycarboxylic acid anhydride per epoxy group and preferably from about0.8 to about 2.5 carboxyl groups per epoxy group. It should be notedthat by the expression carboxyl groups of the polycarboxylic acidanhydride is meant the carboxyl groups which would be contained by thecorresponding polycarboxylic acid. For example, succinic anhydride doesnot possess any carboxyl groups per se; however, the correspondingpolycarboxylic acid is succinic acid which contains two free carboxylgroups. Thus, succinic anhydride has tWo carboxyl groups as applied inthe above expression. In different language, by the expression carboxylgroups of polycarboxylic acid anhydride is meant the carboxyl groupscontained in the hydrated polycarboxylic acid anhydride.

Illustrative polycarboxylic acid anhydrides include the aliphatic,aromatic and cycloaliphatic acid anhydrides. The preferred anhydridesare the dicarboxylic acid anhydrides and preferably the hydrocarbondicarboxylic acid anhydrides which include, for example, phthalicanhydride, tetrahydrophthalic anhydride, maleic anhydride, glutaricanhydride, succinic anhydride, nonenylsuccinic anhydride, 1,8-naphthalicanhydride, lower alkyl substituted-bicyclo [2.2. l]hept--ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-2-ene2,3 dicarboxylic anhydride, and the like. Polycarboxylic acid anhydrideswhich have melting points below about 250 C. are satisfactory; thoseanhydrides possessing melting points below about 200 C. are preferred.

Further novel curable, partially cured, and cured compositions of thesixth and seventh embodiments of the invention comprises homopolymer orcopolymer of 4-oxatetracyclo[6.2.1.0 .0 ]-undec-9-yl unsaturatedderivative and polyol in such relative amounts as provide from about 0.1to about 2.0 hydroxyl groups i.e., -OH groups, of said polyol per epoxygroup of said homopolymer or copolymer epoxide, and preferably fromabout 0.2 to about 1.0 hydroxyl group per epoxy group. By the termpolyol as used herein including the appended claims, is meant an organiccompound having at least two hydroxyl groups, which are alcoholichydroxyl groups, phenolic hydroxyl groups, or both alcoholic andphenolic hydroxyl groups. The term polyol preferably encompasses thepolyhydric alcohols and the polyhydric phenols.

Illustrative of the polyols contemplated include, for example, thealiphatic and cycloaliphatic polyhydric alcohols, e.g., ethylene glycol,diethylene glycol, the polyethylene glycols, propylene glycol, thepolypropylene glycols, the polyethylenepolypropylene glycols,1,1,l-trimethylolpropane, the polyvinyl alcohols, the cyclopentanediols,the cyclohexanediols, the lower alkyl substitutedcyclohexanediols; andthe polyhydric phenols, e.g., resorcinol, catechol,bis(4-hydroxyphenyl)-2,2-propane, 1,8- naphthalenediol, the polyhydricphenolformadlehyde condensation products, and the like. The alkyleneoxide adducts, e.g., ethylene oxide, propylene oxide, etc., ofpolyhydric alcohols or polyhydric phenols such as those illustratedabove also are highly suitable. Polyols having melting points belowabout 250 C. are desirable; those polyols having melting points belowabout 200 C. are preferred.

Additional novel curable, partially cured, and cured compositions of thesixth and seventh embodiments of the invention comprises homopolymer orcopolymer of 4-oxatetracyclo-[621.0 .0 1undec-9-yl unsaturatedderivatives and polycarboxyl polyester in such relative amounts asprovide from about 0.1 to about 2.0 carboxyl groups of said polycarboxylpolyester per epoxy group of said homopolymer or copolymer epoxide, andpreferably from about 0.3 to about 1.2 carboxyl groups per epoxy group.By the term polycarboxy polyester, as used herein including the appendedclaims, is meant a polyester which contains at least two carboxyl groupsin the average molecule. The polycarboxy polyesters can be prepared byknown condensation procedures, employing mol ratios favoring greaterthan equivalent amounts of polycarboxylic acid or polycarboxylic acidanhydrides with relation to the polyhydric alcohol. More specifically,the amount of polycarboxylic acid or polycarboxylic acid anhydride whichis employed in the esterification reaction should contain more carboxylgroups, collectively, than are required to react with the hydroxylgroups contained in the amount of polyhydric alcohol so that theresulting esterified product, i.e. polycarboxy polyester, contains atleast two free carboxyl groups in the average polycarboxy polyestermolecule. The poly carboxylic acids, polycarboxylic acid anhydrides, andpolyols which can be employed in the preparation of the polycarboxypolyesters have been illustrated previously The polycarboxy polyesterscan be obtained by condensing, in accordance with known procedures, apoly hydric alcohol and a polycarboxylic acid or a polycarboxylic acidanhydride. This condensation reaction can be conducted, for example, byheating the reactants to a temperature within the range from C. to 200C. with or without an acidic catalyst. Water formed by the condensationreaction may be removed by distillation. The course of the reaction maybe followed by making acid number determinations and the reaction can bestopped when a suitable polycarboxy polyester has been obtained.

The invention also contemplates the modification of the properties andcharacteristics of the partially cured and fully cured compositions(resins) set forth previously in the discussion. Special and highlydesirable effects can be imparted to the partially cured and fully curedcompositions by incorporating a second active organic hardener(hereinafter termed modifier) into the curable composition comprisingthe homopolymer or copolymer of 4-oxatetracyclo [6.2. 1 .0 .0]undec-9-yl unsaturated derivative and major active organic hardener(i.e., polycarboxylic acid, polycarboxylic acid anhydride, polyol,polycarboxy polyester, and the like). The proportions of modifier tomajor active organic hardener are such that the number of reactivegroups contained by an amount of the modifier with relation to thenumber of reactive groups contained by an amount of the major activeorganic hardener will be in a ratio that is less than one. It is to beunderstood that the term reactive groups pertains to groups which arereactive with the epoxy groups contained in the unsaturated epoxide. Forinstance, to a curable composition comprising the homopolymer orcopolymer of 4-oxatetracyclo [621.0 .0 1 undec-9-yl unsaturatedderivative and polycarboxylic acid, there can be added an amount of amodifier, e.g., polycarboxylic acid anhydride, polycarboxy polyester,polyol, etc., such that the ratio of reactive groups contained by themodifier with respect to the carboxyl groups contained by thepolycarboxylic acid is less than one. On this basis the modifier can beconsidered to be the minor component in relation to the polycarboxylicacid. As a second illustration, if the curable composition comprises ahomopolymer or copolymer of 4-oxatetracyclo [6.2.1.0 .0 ]undec 9 ylunsaturated derivative and polyol, an amount of modifier, e.g.polycarboxylic acid, polycarboxy polyester, polycarboxylic acidanhydride, polyisocyanate, polythiol, etc., can be added to said curablemixture such that the ratio of the reactive groups contained by themodifier with respect to the hydroxyl groups contained by the polyol isless than one. Again it will be noted that the modifier is the minorcomponent with respect to the polyol. The modifiers which can beemployed are those illustrated previously in the discussion ofpolycarboxylic acids, polycarboxylic acid anhydrides, polyols,polycarboxy polyesters, etc.

Other curable, partially cured and cured compositions of the sixth andseventh embodiment of the invention comprise homopolymers or copolymersof 4-oxatetracyclo[6.2.1.0 .O ]undec-9-yl unsaturated derivatives and apolyfunctional amine in such relative amounts so as to provide fromabout 0.2 to about 5.0 amino hydrogen atoms of the polyfunctional amineper epoxy group of the unsaturated epoxide, and preferably from about0.8 to about 2.0 amino hydrogen atoms per epoxy group. By the termpolyfunctional amine as used herein including the appended claims, ismeant an organic amine having at least two active amino hydrogen atomswhich can be on the same nitrogen atom or on different nitrogen atoms.

Among the polyfunctional amine subclasses contemplated include thealiphatic amines, aromatic amines, aralkyl amines, cycloaliphaticamines, alkaryl amines, aliphatic polyamines including polyalkylenepolyamines, amino-substituted monohydric and polyhydric aliphaticalcohols and phenols, polyamines, addition products of polyamines andlow molecular weight epoxides containing oxirane oxygen linked tovicinal carbon atoms, and others.

Illustrative polyfunctional amines include, for example, methylamine,butylamine, Z-ethylhexylamine, aniline, o-hydroxylaniline, meta-, ortho,and para-phenylenediamines, 1,4naphthalenediamine,p-menthane-1,8-diamine, decylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, andthe like. The polyamines, i.e., those having an average molecular weightrange from about 300 to about 10,000 including condensation products ofpolycarboxylic acids, in particular, hydrocarbon dicarboxylic acids,such as malonic acid, succinic acid, glutaric acid, adipic acid,dilinoleic acid, and the like, with polyamines, particularly diamines,such as ethylenediamine, propylenediamine, butylenediamine and the likeare also suitable.

In the following illustrative examples, the examination and descriptionof the resins were conducted at room temperature, i.e., about 24 C.

Example 1 A solution (202 grams) of peracetic acid (28.7 weight percent)in ethyl acetate was added dropwise over a period of 45 minutes to 290-grams of allyl tricyclo [5.2.1.0 ]dec-3-en-8-yl ether at 30 C. After anadditional three-hour reaction period at 30 C., an analysis indicatedthat all of the peracetic acid had been consumed. The reaction productmixture was fed dropwise to a still kettle containing 600 grams ofethylbenzene under reflux at such a pressure as to maintain a kettletemperature of 50 C. The ethyl acetate, acetic acid and some of theethylbenzene were removed continuously at the still head during theaddition. After removal of the remaining ethylbenzene, the reactionproduct was distilled under reduced pressure. There was obtained 132grams (84 percent yield) of allyl 4 oxatetracyclo[6.2.1.0 .O ]undec-9-ylether, a colorless liquid having the following properties:

Boiling point116-l18 C. at 2 milliliters Hg Refractive index (n30/D)-l.50001.5004 Purity by epoxide analysis (HBr)100.5% Percentcarbon-75.22 (calc. 75.68%) Percent hydrogen-8.89 (calc. 8.79%)

In an analogous manner as the above example 4-oxatetracyclo[6.2.1.0 .0]undec-9-yl propyl ether is prepared.

Example 2 A solution of 19.3 grams of N-(tricyclo[5.2.1.0 ]dec-3-en-8-yl) acrylamide in 80 grams of acetone was heated to 50 C. withstirring to eifect solution. To this solution was added 40.7 grams of a28 weight percent solution of peracetic acid in ethyl acetate over aperiod of one hour while maintaining the temperature at 50 C. Thesolution was heated for an additional seven hours at 50 C., at whichtime, an analysis indicated that 96 percent of the theoretical amount ofperacetic acid had reacted. The solution was cooled to 10 C., andfiltered to obtain 10 grams of N-(4-oxatetracyclo[6.2.1.0 ".0 ]undec 9yl) acrylamide, a white crystalline solid, M.P. 152 C. Evaporation ofthe filtrate, cooling, and filtering gave a second crop (4 grams) ofcrystals. The yield was, therefore, 67 percent of the theoretical.

A portion of the crystalline product, N-(4-oxatetracyclo [6.2.1.0 .0]undec 9 yl)acrylamide was recrystallized twice from ethyl acetate togive a white crystalline solid having the following properties:

Melting point-1S2-3 C.

'1 4 Percent nitrogen-6.43 (calc. 6.38%) Percent carbon70.6% (calc.71.9%) Percent hydrogen7.73% (calc. 7.75%)

The infrared spectrum of the product still contained the bandscharacteristic of the terminal double bond in the starting material. Inaddition, there was a strong band at 11.92 microns which is the regioncharacteristic of cis epoxides.

In an analogous manner as the above example, N-(4- oxatetracyclo[6.2.1.0.0 undec 9 yl)propionamide is prepared.

Example 3 A mixture of 258 grams of 3-butenoic acid, 396 grams oftricyclo[5.2.1.0 -3,8-decadiene and 25 grams of borontrifluoride-etherate was stirred at 60 C. for five hours. The mixturewas cooled, diluted with 300 milliliters of toluene, washed with 250milliliters of water, then washed with dilute soda solution and againwith water. The oil layer recovered was dried over sodium sulfate anddistilled under reduced pressure. The ester distilled at 112 C. (1.5millimeters Hg) as a colorless liquid having a refractive index (D-line)at 30 C. of 1.4972. The yield was 478 grams (73 percent) oftricyclo[5.2.1.0 ""]dec-3- en-8-yl 3-butenoate.

Analysis.Calcd. for C I-1 0 C, 77.03; H, 8.31. Found: C,76.80; H, 8.30.

Example 4 A solution (1025 grams) of peracetic acid (24.1 weightpercent) in ethyl acetate was added dropwise with stirring to 394 gramsof tricyclo[5.2.1.0 ]dec-3-en-8-yl 3-butenoate at 50 C. over a period of2 hours. After 2 additional hours at 50 C., the temperature of thereaction mixture was raised to 60 C. and maintained there for anadditional 5 hours. At this time, approximately percent of thetheoretical amount of peracetic acid was consumed.

The reaction product mixture was fed dropwise into a still kettlecontaining ethylbenzene refluxing under such a pressure to maintain thekettle temperature at 50 C. Ethyl acetate, acetic acid, excess peraceticacid and some ethylbenzene were removed continuously at the still headthroughout the addition. After removal of the ethylbenzene, the reactionproduct Was fractionated to give 2.18 grams (51 percent) of4-oxatetracyclo[6.2.l.0 .0 undec-9-yl- 3-butenoate having a boilingpoint of C. (0.04 millimeters Hg) and a refractive index (D-line) at 30C. of 1.50011.5028. An epoxide analysis (pyridine hydrochloride method)indicated a purity of 95.4%.

Example 5 To 337 grams of tricyclo[5.2.1.0 ]-8-chloro-3-decene which wasmaintained with stirring at 40 C. by means of an ice-water bath, therewas added dropwise over a period of two hours and fifteen minutes 683grams of a 27.9 weight percent solution of peracetic acid in ethylacetate. After an additional three hours and fifteen minutes at 40 C.,the reaction was essentially complete as indicated by a titration forperacetic acid. The volatiles were removed from the solution bycodistillation With ethylbenzene and the residue was fractionated togive 333 grams of 4-oxatetracyclo[621 .0 ]-9-chloroundecane having thefollowing properties:

Boiling point80-82/0.100.15 millimeters Refractive index-n/ 30D15204-15206 Analysis.Calcd. for C H ClO; C, 65.20; H, 7.09. Found: C,65.19; H, 6.86.

Example 6 n-Butyl tricyclo[5.2.1.0 ]dec-3-en-8-yl sulfiide was preparedin 88.9 percent yield by the addition of n-butyl mercaptan totricyclo[5.2.1.0 ]-3,8-decadiene. n-Butyl tricyclo[5.2.1.0]-dec-3-en8-yl sulfide was a colorless 15 liquid boiling at 125127 C. at2 millimeters Hg and having a refractive index range of 1.52081.5224(N30/D).

Analysis.-Calculated for C H S: S, 14.42%. Found: S, 14.40%.

n-Butyl tricyclo[5.2.1.0 dec-3-en-8-yl sulfide was converted to thecorresponding sulfone by reaction with a 5 percent excess of peraceticacid solution in ethyl acetate at -10 C. The product, n-butyltricyclo[5.2.1.0 ]dec- 3-en-8-yl sulfone, which was isolated in 89percent yield by distillation, was a colorless liquid having a boilingpoint of 172173 C. at 3 millimeters Hg and a refractive index range of15185-15194 (N30/D).

Analysis.Calculated for C H SO S, Found: S, 12.59%.

To n-butyl tricyclo[5.2.1.0 ]dec-3-en-8y1 sulfone (442 grams) was added573 grams of a 28.8 weight percent solution of peracetic acid in ethylacetate over a onehour period at 50 C. After an additional 2.25-hourreaction period at 60 C., the consumption of peracetic acid was 97.5percent of the theoretical. The reaction product was isolated bycodistillation of the volatiles with ethylbenzene under reduced pressurefollowed by stripping at a kettle temperature of 100 C. at 6 millimetersHg. The product, n-butyl 4-oxatetracyclo[621.0 .0 ]undec-9- yl-sulfone,was a pale-yellow liquid having a refractive index of 1.5200 (N30/D).

Analysis.Calculated for C H SO Found: S, 11.57%.

Example 7 n-Dodecyl tricyclo[5.2.1.O ]dec-3-en-8-yl sulfide was preparedin 80.8 percent yield by the addition of n-dodecyl sulfiide totricyclo[5.2.1.O ]-3,8-decadiene. n-Dodecyl tricyclo[r5.2.1.0]dec-3-en-8-yl sulfide was a liquid boiling at 202-208 C. at 2millimeters Hg and having a refractive index range of 1.49961.5009(N30/D).

Anaylsis.Calculated for C H S: S, 9.59%. Found: S, 9.56%.

n-Dodecyl tricyclo[5.2.1.0 ]dec-3-en-8-yl sulfide (411 grams) wasdissolved in 657 cubic centimeters of ethyl acetate and to this solutionwas added 657 grams of a 29.8 weight percent solution of peracetic acidin ethyl acetate over a 2-hour period at 010 C. The reaction mixture wasreduced in volume by removing approximately one half of the ethylacetate, cooling said reaction mixture in a brine bath (10 C.), andfiltering the white crystalline solid. The solid product, n-dodecyltricyclo- [5.2.1.0 ]dec-3-en-8-yl sulfone, was recrystallized from 400cubic centimeters of ethyl acetate obtaining 363 grams of whitecrystalline solid having a melting point of 51-52 C. An additional 47grams of product was recovered from the mother liquor making a totalyield of 91.6 percent.

Arzalysis.Calculated for Found: S, 8.81%.

n-Dodecyl tricyclo[5.2.1.0 dec-3-en-8-yl sulfone (363 grams) wasdissolved in 300 grams of ethyl acetate, and to this solution was added336 grams of a 28.8 weight percent solution of peracetic acid in ethylacetate over a 1.25-hour period. After an additional reaction period ofhours at 60 C. the solution was allowed to stand overnight at roomtemperature. The reaction product mixture was cooled in a DryIce-acetone bath, and the white crystalline solid was filtered. Aftertwo recrystallizations from ethyl acetate, there was obtained a 79.8percent yield of white crystals of n dodecyl 4 oxatetracyclo-[6.2.1. 0.0 ]undec-9-yl sulfone melting at 90.5-91.5 C.

Analysis.Calculated for C H SO S, 8.38%. Found: S, 8.28%. Epoxidepurity: 95%.

Example 8 To a pyrex 'tube'there is charged 1.0 gram N-(4-oxatetracyclo[6.2. 1 0 .0 undec-9-yl) acrylamide, 9.0 grams vinyl chloride, 5.0milliliters acetone, and 1.0 milliliter of a 25 percent solution ofacetyl peroxide in dimethyl 16 phthalate. The tube is purged withnitrogen, sealed, and rocked in a water bath at 50 C. for 22 hours. Thepolymer recovered is cast as a film from a cyclohexanone solution of thepolymer containing one percent phosphoric acid (based on resin weight).The film is cured at C. for 5 hours. There is formed an insoluble,infusible polymer.

Example 9 To a Pyrex tube there is charged 15.0 grams4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl 3-butenoate, 5 .0 grams ethylacrylate, and 1.0 milliliter of a 25 percent solution of acetyl peroxidein dimethyl phthalate. The tube is purged with nitrogen, sealed androcked in a water bath at 50 C. for 43 hours. The recovered polymer is afusible resin.

Example 11 To a Pyrex tube there is charged 8 grams4-oxatetracyclo[6.2.1.0 .0 ]undec-9-yl allyl ether, 2.0 gramschlorostyrene, and 2.0 milliliters of a 25 percent solution of acetylperoxide in dimethyl phthalate. The tube is purged with nitrogen, sealedand rocked in a water bath at 50 C. for 22 hours. The polymer recoveredis cast as a film from a cyclohexanone solution of the polymercontaining one percent phosphoric acid (based on resin weight) The filmis cured at 100 C. for 5 hours. There is formed an insoluble infusiblepolymer.

Example 12 To a Pyrex tube there is charged 10.0 grams4-o'xatetracyclo[6.2.1.0 .0 ]undec-9-yl allyl ether, and 2.0 millilitersof a 25 percent solution of acetyl peroxide in dimethyl phthalate. Thetube and contents are heated at 100 C. for 17 hours. The resultingproduct is a fusible homopolymeric product. This fusible polymericproduct is heated at a temperature of 100 C. for 5 hours in the presenceof 0.5 gram of boron trifiuoride-monoethylamine complex to obtain ahard, infusible, thermoset resin.

Example 13 4-oxatetracyclo[6.2.l.0 .0 ]undec-9 yl 3 bute'noate (10grams) is mixed with 0.5 gram of boron trifluoridemonoethylamine complexand heated to 70 C. for 7 hours. The resulting product is a fusiblehomopolymeric product. The homopolymeric product is heated to 75 C. for4 hours in the presence of 1.0 milliliter of a 25 percent solution ofbenzoyl peroxide in dimethyl phthalate to obtain a hard, thermoset,infusible product.

Example 14 N (4 oxatetracyclo[6.2.1.0 .0 ]undec-9-yl)-acrylamide (10grams) is mixed with 0.05 gram of benzoyl peroxide and heated at 100 C.for 12 hours. A fusible productis obtained. The fusible product andcitraconic acid are admixed in amounts so as to provide 0.8 carboxylgroup of said acid per epoxy group of the fusible product. The resultingadmixture then is heated to C. for 5 hours plus an additional 6 hours atC. There is obtained a hard resin.

Example 15 Allyl 4 oxatetracyclo[6.2.1.0 ".0 1undec 9 yl ether (10grams) is mixed with 0.05 gram of benzoyl peroxide and heated at 100 C.for 12 hours. A fusible product is 17 obtained. This fusible product andphthalic anhydride are admixed in amounts so as to provide 0.8 carboxylgroup of said anhydride per epoxy group of the fusible product. Theresulting admixture then is heated to 120 C. for 5 hours plus anadditional 6 hours at 160 C. There is obtained a hard resin.

In an analogous manner as above when the initial polymerized product of5-hexenyl 4-oxatetracyclo- [6.2.1.0 .0 ]undec-9-yl ether and 4oxatetracyclo- [6.2.1. .0 ]undec-9-yl undecylenate, 4 oxatetracyclo-[6.2.1.0 are admixed individually with succinic anhydride in amounts soas to provide 1.0 carboxyl group of said anhydride per epoxy group ofsaid polymerized product, followed by curing the resulting admixtureunder essentially similar operative conditions, there are obtained ineach case a hard, infusible resin.

Example 16 4-oxatetracyclo[6.2.1.0 .0 ]undec-9 yl 3 butenoate (30 grams)is mixed with 0.15 gram of benzoyl peroxide and heated at 100 C. for 14hours. A fusible product is obtained. This fusible product and adipicacid are admixed in amounts so as to provide 0.6 carboxyl group of saidacid per epoxy group of said fusible product. The resulting mixture isthen heated to 120 C. for 6 hours plus an additional hours at 160 C.There is obtained a hard resin.

Example 17 N (4 oxatetracyclo[6.2.1.0 ]undec-9-yl)-acrylamide (30 grams)is mixed with 0.15 gram of benzoyl peroxide and heated at 100 C. for 12hours. A fusible product is obtained. This fusible product and sebacicacid are admixed in amounts so as to provide 1.0 carboxyl group of saidacid per epoxy group of said fusible product. The resulting admixture isthen heated to 120 C. for 6 hours plus an additional 6 hours at 160 C.There is obtained a hard resin.

Example 18 The compound, allyl 4-oxatetracyclo[6.2.1.0 *".0 ]un dec-9-ylether (30 grams) is mixed with 0.15 gram of henzoyl peroxide and heatedat 100 C. for 14 hours. A fusible product is obtained. This fusibleproduct and bis- (4-hydroxyphenyl)-2,2-propane are admixed in amounts soas to provide 1.0 hydroxyl group of saidbis(4-hydroxyphenyl)-2,2-propane per epoxy group of said fusibleproduct. The resulting admixture is then heated to 120 C. for 6 hoursplus an additional 5 hours at 160 C. There is obtained a hard resin.

Example 19 The compound, N-(4-oxatetracyclo[6.2.1.0 .0]-undec-9-yl)acrylamide (30 grams), is mixed with 0.15 gram of benzoylperoxide and heated at 100 C. for 14 hours. A fusible product isobtained. This fusible product and resorcinol are admixed in amounts soas to provide 1.0 hydroxyl group of said resorcinol per epoxy group ofsaid fusible product. The resulting admixture is then heated to 120 C.for 6 hours plus an additional 5 hours at 160 C. There is obtained ahard resin.

Example 20 The compound, 4-oxatetracyclo[6.2.1.0 .0 ]undec-9- yl3-butenoate (30 grams) is mixed with 0.15 gram of benzoyl peroxide andheated at 100 C. for 14 hours. A fusible product is obtained. Thisfusible product and adipic acid are admixed in amounts so as to provide1.0 carboxyl group of said acid per epoxy group of said fusible product.The resulting product is dissolved in methyl isobutyl ketone at 100 C.,and an iron panel is dipped into the resulting solution. The iron panelsubsequently is removed from this solution, is air dried for 15 minutes,and is baked at 160 C. for 2 hours. A thin coating is observed on thatportion of the dipped iron panel. The resulting coating on the panel isglossy and tough. The coating displays excellent adhesion to the panel.

Example 21 To a Pyrex tube there is charged 1.0 gramN-(4-oxatetracyclo[621 .0 ]undec-9-yl)acrylamide, 9.0 grams vinylchloride, 5.0 milliliters acetone, and 1.0 milliliter of a 25 percentsolution of acetyl peroxide in dimethyl phthalate. The tube is purgedwith nitrogen, sealed and rocked in a Water bath at 50 C. for 22 hours.The polymer is recovered and phthali-c anhydride is admixed with it inan amount so as to provide 0.8 carboxyl group of said anhydride perepoxy group of the polymer product. The resulting admixture then isheated to C. for 5 hours plus an additional 6 hours at C. There isobtained a hard resin.

Example 22 To a Pyrex tube there is charged 5.0 grams allyl 4-oxatetracyclo[6.2.1.0 0 ]undec-9-yl ether, 5.0 grams acrylonitrile, 5.0milliliters acetone, and 1.0 milliliter of a 25 percent solution ofacetyl peroxide in dimethyl phthalate. The tube is purged with nitrogen,sealed and rocked in a water bath at 50 C. for 14 hours. The polymer isrecovered and adipic acid is admixed with it in an amount so as toprovide 0.6 carboxyl groups of said anhydride per epoxy group of thepolymer product. The resulting admixture then is heated to 120 C. for 5hours plus an additional 6 hours at 160 C. There is obtained a hardresin. 1

Example 23 To a Pyrex tube there is charged 5.0 gramN-(4-0xatetracyclo[6.2.l.0 10 undec-9-yl)acrylamide, 5.0 grams ethylacrylate, 5.0 milliliters acetone, and 1.0 milliliter of a 25 percentsolution of acetyl peroxide in dimethyl phthalate. The tube is purgedwith nitrogen, sealed and rocked in a water bath at 50 C. for 43 hours.The polymer is recovered and catechol is admixed with it in an amount soas to provide 1.0 hydroxyl group of said catechol per epoxy group of thepolymer product. The resulting admixture then is heated to 120 C. for 5hours plus an additional 6 hours at 160 C. There is obtained a hardresin.

Example 24 To a Pyrex tube there is charged 8.0 grams4-0xatetracyiclo[621.0 .0 ]undec-9-yl 3-butenoate, 2.0 gramschlorostyrene, 5.0 milliliters acetone, and 1.0 milliliter of a. 25 percent solution of acetyl peroxide in dimethyl phthalate. The tube ispturged with nitrogen, sealed and rocked in a water bath at 50 C. for 17hours. The polymer is recovered and glycerol is admixed with it in anamount so as to provide 1.0 hydroxyl group of said glycerol per epoxygroup of the polymer product. The resulting admixture t-hen is heated to120 C. for 5 hours plus an additional 6 hours at 160 C. There "isobtained a hard resin.

What is claimed is:

1. A monoepoxide having the general formula:

wherein Y represents a member selected from the group consisting ofhalo, RO,

and R'SO wherein R represents a hydrocarbon radical, which is free ofacetylenic unsaturation, with the proviso that when R in the RO- groupis an alkenyl moiety, the ethylenically unsaturated carbon to carbonbond is at least one carbon atom removed from the ether oxygen atom; andwherein R represents a saturated hydrocarbon radical.

2. Alkenyl 4-oxatetracyclo[6.2.1.0 .0 ]undec 9 yl ether wherein theethylenic group of the alkenyl radical is at least one carbon atomremoved from the ether oxygen atom.

3. N (4-oxatetracyclo[6.2.1.0 .0 ]undec-9 y1)alkanamide.

4. N (4-oxatetracyclo[6.2.1.0 .0 ]undec-9-y1)alkenaniide.

5. Allyl 4-oxatetracyclo[6.-2.1.O ..0 ]-undec 9 yl ether.

6. 4-oxatetracyc1o[6.2.1.0 '0 ]undec 9 yl propyl ether.

7. N (4 oxatetracyc-lo[6.2.1.0 .O ]undec-9-y1)acrylamide.

8. N-(4-oxatetracyc1o[6.2.1.03- .0 ]undec 9 yl)propionamide.

9. A homopolymer of the monoepoxide having the gen- 613.1 formula.

wherein Y represents a member selected from the group consisting ofR-O-, and

wherein R represents an unsaturated hydrocarbon radical, which is freeof .acetylenic unsaturated hydrocarbon radical, which is free ofacetylenic unsaturation with the proviso that the ethylenicallyunsaturated group in R of the R-O- group is at least one carbon atomrecoved from the ether oxygen atom.

10. A homopolymer of alkenyl 4 oxatetracyolo [6.2.1.0 .0 ]undec-9-ylether wherein the ethylenically unsaturated carbon to carbon bond is atleast one carbon atom removed from the ether oxygen atom.

11. The homopolyer of claim 9 wherein the polymerization occurs throughthe epoxy groups.

12. The homopolymer of claim 9 wherein the polymerization occurs throughthe ethylenically unsaturated carbon to carbon bond.

13. A copolymer resulting from the polymerization reaction of amonoepoxide having the general formula:

wherein Y represents a member selected from the group consisting of R-O,and

References Cited by the Applicant UNITED STATES PATENTS 2,324,483 7/1943 Caston 260-47 2,393,610 1/1946 Bruson 260-611 2,543,419 2/ 1951Niederhauser 260-2 2,962,453 11/1960 Philips 260-348 2,962,469 11/1960Phillips et a1. 260-454 3,031,439 4/1962 Bailey 260-2 3,040,010 6/1962Shokal et a1. 260-2 3,066,151 11/1962 Thorne et a1 260-348 OTHERREFERENCES Noller, C.R., Chemistry of Organic Compounds pp. 59, 101,137, 229, 245, 278-9, W. B. Saunders C0., Philadelphia, 1957 (Copy inGroup Bruson et a1. J.A.C.S. vol. 68 January 1946 pages 8-10 (Copy inSci. Lib.) 260-6111 JOSEPH L. SCHOFER, Primary Examiner. MILTON STERMAN,J. R. LIBERMAN, Examiners.

1. A MONOEPOXIDE HAVING THE GENERAL FORMULA:
 13. A COPOLYMER RESULTINGFROM THE POLYMERIZATION REACTION OF A MONOEPOXIDE HAVING THE GENERALFORMULA: